TW414813B - Deposition of copper with increased adhesion - Google Patents

Deposition of copper with increased adhesion Download PDF

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Publication number
TW414813B
TW414813B TW088102874A TW88102874A TW414813B TW 414813 B TW414813 B TW 414813B TW 088102874 A TW088102874 A TW 088102874A TW 88102874 A TW88102874 A TW 88102874A TW 414813 B TW414813 B TW 414813B
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TW
Taiwan
Prior art keywords
copper
scope
item
patent application
layer
Prior art date
Application number
TW088102874A
Other languages
Chinese (zh)
Inventor
Zheng Bo
Ling Chen
Alfred Mak
Mei Chang
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Applied Materials Inc
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Publication of TW414813B publication Critical patent/TW414813B/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • C23C16/0245—Pretreatment of the material to be coated by cleaning or etching by etching with a plasma
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/08—Copper compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C23C16/0281—Deposition of sub-layers, e.g. to promote the adhesion of the main coating of metallic sub-layers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
    • H01L21/76855—After-treatment introducing at least one additional element into the layer
    • H01L21/76856—After-treatment introducing at least one additional element into the layer by treatment in plasmas or gaseous environments, e.g. nitriding a refractory metal liner
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
    • H01L21/76876—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for deposition from the gas phase, e.g. CVD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Plasma & Fusion (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Electrodes Of Semiconductors (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

A method and apparatus for improving the adhesion of a copper layer to an underlying layer on a wafer. The layer of copper is formed over a layer of material on a wafer and the copper layer impacted with ions to improve its adhesion to the underlying layer.

Description

414813 五、 發明説明（ A7 B7 經濟部智毪財4¾員工消費合作社印賢 t明領域： 本發明關於製造積體電路之領域。 '現在，鋁已經廣泛地使用於積體電路之中’作為一内 '線例如插塞及接線。然而，更高元件密度，更快操作 頻率’及更大晶粒尺寸已經增h 了對具有較銘為低之電阻 率金屬之需求，以使用作為内連線結構中。銅之低電阻率 使得其作為替代鋁之最佳候選。 使用銅替代鋁之一挑戰是鋼乾蝕現在並不可行。例如 化學機械研磨之研磨處理係被使用以去除銅沉積層之不 想要部份。使用化學機械研磨之需求呈現了-挑戰，因為 銅1對現行於銅底下用以作為擴散阻障層之材料，具有較差 之附著能力。對於沉積於擴散阻障層上之銅之研磨因此可 能造成部份之銅不想要地被剌離開擴散阻障層之表面。這 使得積體電路成劣品。 當沉積銅時，吾人想要使用相對於物理氣相沉積之化 學氣相沉積（CVD)，因為CVD提供了更保角層之銅層。然 而’銅之化學氣相沉積代表了另—挑戰。該挑戢係由於當 鋼沉積時所產生之副產物。 於一例子中，銅之化學氣相沉積係藉由使用被稱為卡 巴捨力（Cupraselect)之前驅物加以完成，其具有公式為 Cu(hfac)L。L代表路易氏基化合物，例如三甲基矽烷乙缔 脂（VTMS) 〇 hfac代表六氟乙埽丙嗣及Cu代表铜。於使用 第4頁 本紙張尺度適用中國國家標準（CNS ) ,\4说格（210 -<297公發） ---- ----Λ..---^----ix------•線 (請先ί、背面之注意事項再填寫本頁) 414813 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（414813 V. Description of the invention (A7 B7 Ministry of Economic Affairs, Intellectual Property, Finance and Economics) ¾ Employee Consumer Cooperative Association Yinxiant Field: The present invention relates to the field of manufacturing integrated circuits. 'Now, aluminum has been widely used in integrated circuits' as a Inner wires such as plugs and wiring. However, higher component densities, faster operating frequencies, and larger grain sizes have increased the need for metals with lower resistivity than the nominal, to be used as inner wires In the structure, the low resistivity of copper makes it the best candidate to replace aluminum. One of the challenges of using copper instead of aluminum is that dry etching of steel is not feasible now. For example, chemical mechanical polishing is used to remove copper deposits. Unwanted parts. The need to use chemical mechanical polishing presents a challenge, because copper 1 has a poor adhesion to the materials currently used as diffusion barriers under copper. For copper deposited on diffusion barriers Grinding may therefore cause some copper to be undesirably removed from the surface of the diffusion barrier layer. This makes the integrated circuit inferior. When depositing copper, we want to use relative Chemical vapor deposition (CVD) in physical vapor deposition, because CVD provides a more conformal layer of copper. However, chemical vapor deposition of copper represents another challenge. This challenge is due to the fact that when steel is deposited, By-products are produced. In one example, the chemical vapor deposition of copper is accomplished by using a precursor known as the Cupraselect (Cupraselect) precursor, which has the formula Cu (hfac) L. L represents the Lewis base Compounds, such as trimethylsilyl ethylene glycol (VTMS) 〇hfac stands for hexafluoroacetamidine and Cu stands for copper. For use on page 4, this paper applies Chinese National Standard (CNS). < 297 public hair) ---- ---- Λ ..--- ^ ---- ix ------ • line (please first, please note on the back before filling this page) 414813 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

Cu(hfac)前驅物作為CVD時，前驅物係被、;气化並被流入一 含晶圓之沉積室中。於該室中’前驅物係以熟能滲入於晶 圓表面’及造成以下之反應式： 2Cu(hfac)L—Cu十Cu(hfac)2 + 2L (反應弋 ι) 所得之鋼（C11)沉積於晶圓之上表面，以及，有 Cu(hfaCh副產物。氣體路易氏基副產物（2l)係由室中排 除。副產物及其他於晶圓表面上之污染物之出現，降低了 銅對下擴散阻障層，例如氮化担之附著力。 為了改反鋪對下層擴散阻障層之附著力，用以沉積銅 之製程係被分成兩步驟。於第一步驟中， 物理氣相沉積 (PVD)係被執行，以沉積銅之晶種層3於pVD中，一銅纪 係被置於基板上’其上係被沉積以飼。—氣氣係被引入於 銅乾及基板間之環境中。氬氣然後被經由射頻（rf)信號之 使用而被激勵，以創造出含離子之電漿》 來自電漿之離子碰撞銅靶，藉以分解鋼之粒子，而沉 積於基板上。這些銅粒子係大致被離子化並因此為高能。 此高能鋼離子能良好附著至阻障層。基板係被偏壓，使得 一電壓梯度被形成於靶及基板之間，藉以造成銅離子加速 該梯度並轟擊該基板。轟擊之結果，銅粒子強烈地附著至 基板之表面。第二，此PVD製程提供了於銅晶種層及阻 障層間之乾淨界面。 一旦銅之晶種層使用P V D而沉積，則一主材質銅層 係被沉積。主材質層係藉由標準化學氣相沉積或電鍍加以 沉積。銅之主材質層相當良好地附著至铜晶種層。 第5頁 本紙張尺度適用中國國家榡準（CNS ) Λ4規格（2丨OX297公漦） ---- ----,,---^----,訂------^ * (請先閱讀背面之注意事項苒填寫本頁) 414813 A7 一 B7 五、發明説明（） 然而’ PVD製程之使用造成了較差之階梯覆蓋，這對 於小特性之裝置是不可接受的。再者，PVD製程不能於化 學氣相沉積室或電鍵之同一室中完成。由於需要一 PVD 室及不是CVD就是電鍍室’而增加了積體電路製造成本。 因此，吾人想要提供保角化學氣相沉積鋼至擴散阻障 層上，使得於銅及下層擴散阻障層間之附著力得以改良。 吾人同時也希望此一沉積可以被進行於單一室中（原處）。 吾人更想要於銅沉積時，降低污染副產物之產生，使得沉 積可以以較少量之前驅物及更快進行。 月概要·‘ 依據本發明’一層例如銅之材料層係被以具有改良附 之方式开）成於晶圓表面上。於形成銅層時，一鋪晶種 首先形成於晶圓之表面上。一旦晶種層被沉積，則銅 以離子轟擊（退火），以改良銅對晶圓表面之附著力。 更明白地說，於惰性氣體之電漿中之離子轟擊銅’以 附著力，這造成铜被”安裝”於晶圓之表面上。這安裝 了銅對晶圓表面之附著力。另外，此轟擊平坦化了銅 而改良了電荷之遷移率。該電漿係被產生於使用惰 體’例如氬之本發明之實施例之中。或者，氫可以配 性氣體使用，以產生轟擊銅之電漿，及提供污染物排 气之加入提供了對於例如碳，氧，氟等之銅沉積副產 去除’藉以加強銅對阻障層之附著力3 ----- ------^---^----訂 — -----線 (請先閱讀背面之注意事項再填荇本頁) 著力 層係 係被 改良 増知 晶fe 性氣 合惰 除。 物之 經濟部智慧財產笱員工消費合作社印製 本纸張尺度 第6頁 (CNS ) A4規格（2丨0X297公趁 414813 A7 B7 五、發明説明（) 圖式簡單說明： 本發明之其他細節係以附圖加以解釋，圖中： 第1圖為一執行依據本發明之沉積銅層之操作順序。 第2(a)-2(d)圖為一依據本發明之銅層之沉積。 第3圖例示出依據本發明之沉積銅之沉積室= 第4圖為一控制系統，其用以依據本發明控制沉積室，該 室係用以依據本發明沉積銅。 圖號對照說明： 一請先閱讀背面之注意事項再填ϊκ:本頁) 經濟部智慧財產笱8工消費合作社印製 110 基 板 111 絕 緣 層 1 12 擴 散 阻 障 層 113 晶 種 層 1 14 電 漿 115 最 終 銅 層 1 16 通 孔 120 CVD 系 統 12 1 氣 體 面 板 122 液 體 面 板 126 信 號 源 127 混 合 方 塊 128 蒸 發 器 129 喷 氣 頭 130 晶 圓 支 撐 13 1 壁 面 132 絕 緣 器 135 壓 力 控 制 單 元 137 處 理 室 140 晶 圓 200 控 制 單 元 205 處 理 機 單 元 2 1 0 記 憶 體 220 大 量 儲存 裝 置 230 加 熱 元 件 250 顯 示 單 元 270 輸 入 控 制 早疋 第7肓 本紙張尺度適用中國國家標準（CNS ) Λ4規格（2ΐϋΧ297公釐） 經濟部智惡財產笱員工"費合作社印製 414813 A7 _ B7 五、發明説明（） 發明詳細說明： 第1圖例示出依據本發明沉積銅於晶圓表面之操作順 序。首先，於步驟100中，一晶種層同係沉積於晶圓之上 表面'晶種銅廣係使用化學氣相沉積法加以沉積，並可以 沉積為連續或不連續銅層。依據本發明，Cu(hfac)L前驅 物係被使用於晶種層之沉積中。然而，其他銅前驅物配合 上還原W]可以用以形成晶種層，例如Cu + 2(hfac)L前驅物 及氫還原劑。 一旦晶種铜層被沉積，則於步驟1 〇 1中，晶種層係被 以電漿處理。電漿係藉由施加RF能量至一或多數氣體而 產生。於本發明之一實施例中’電漿氣體只包含單一氣 體，例如氬，氪或氙。於本發明之另一實施例中，氣體混 合物包含多數氣體，例如氬及氫，氪及氫或氙及氣之組 合。 於電漿處理時’已經沉積有銅之基板需要一偏壓。偏 壓導致於電漿中之離子被加速向基板。這些離子衝擊銅曰曰 種膚’藉以使得銅附著至基板之表面，即銅晶粒變成M安 裝"於基板上，同時平坦化晶粒，以改良電荷之遷移率。 這加強了銅晶種層之附著至基板。同時，若氫離子呈現於 電漿中，其組合前驅物污染副產物並被由室中除去。 一旦電漿處理被完成於步騾101中，則—主材質之鋼 沉積係被執行於步驟1 02中。於主材質沉積時，所沉積之 銅係被沉積於電漿處理過銅上，以形成具有想要厚度及對 晶圓表面有改良附著力之銅層。主材質沉積係使用—化爆 第8頁 尺度辟鮮（CNS i Λ4祕（公廣) — - ---T---^----裝------訂------線 〈請先聞讀背面之注意事項再填^:^頁) 414813 at _ _ -__Β7 五、發明説明（） 氣相沉積以Cu(hfac)L或其他主材質銅沉積處理加以完 成。 於本發明之一實施例中，銅晶種層沉積，電漿處理及 主材質沉積係被完成於單一室中，該室係能執行化學氣相 沉積及電衆處理。因此，銅層係被以原處加以完全形成3 於本發明之其他實施例中，化學氣相沉積及電漿處理係被 執行於不同室中。 弟2(a)-2(d)圖例示依據本發明之積體電路之銅層之 形成。第2(a)圖示出一已經形成（被蝕刻）於絕緣材料（例如 二氧化碎）層1 1 1中之通孔1 1 6。絕緣材料層1 11重疊於基 板110上’其係能電氣耦合至積體電路中之其他元件。基 板11 〇係藉由一内連線結構被連接至其他元件，該内連線 結構將被形成在通孔11 6之中》 絕緣層111之材料之上表面及於通孔116園周内之基 板11 〇之上表面係被一擴散阻障層π 2所覆蓋。擴散阻障 層π 2係被用以禁止内連線結構金屬擴散進入基板1丨〇。 於本發明之一實施例中，内連線結構金屬是銅，及擴散阻 障層是一耐火金屬或耐火金屬氮化物。例如，耐火金屬氮 化物較佳為氮化钽，但也可以是氮化鈦’鈕，氮化鶴或其 他合適以作為於金屬（例如铜）及基板110間之擴散阻障層 之材料。 第2(b)圖例示一铜晶種層1 1 3之沉積，其係可以用於 一内連線結構中。銅晶種層11 3係使用化學氣相沉積法沉 積於擴散阻障層112之上表面。於本發明之一實施例中， __ 第θ貫 本紙張尺度適用標準Tcns ) Λ4規格（~— A請先閱讀背面之注意事0再填均本頁 .装· 線 經濟部智慧財產笱33>'工消費合作社印t 414813 A7 B7 五、發明説明（) 如於第2(b)圖所示，銅晶種層1 13係被沉積為不連續，即 於沉積區域間有間隙。於另一實施例中（未示出），銅晶種 層11 3係被連績沉積’至範囷1 〇埃至3 〇〇埃之厚度。晶 種層之厚度取決於用以處理晶種層之電漿處理參數。因 此，沉積之厚度應配合所選擇之處理參數。 晶種層1 Π之化學氣相沉積係較佳使用Cu(hfac)L前 盤物加以完成，L為VTMS。液體Cu(hfac)L係被汽化， 並流入含擴散阻障層11 2之環境中。前驅物之汽化可以藉 由”經前驅物而11發泡”氮或氫加以完成。汽化前驅物係被以 約〇 1至1 seem之流速提供至該環境。該環境係被控制， 使得其具有於範圍〇_5毫拕耳至丨.5毫托耳之壓力，及基 板係於1 5 0 °C至2 5 0 °C之溫度範圍中。沉積處理係被執行 由3 0秒至5分鐘範園内之時間段中’這是取決於晶種層 之想要厚度。晶種層可以使用其他銅前驅物，例如When Cu (hfac) precursor is used as CVD, the precursor is vaporized and flowed into a wafer-containing deposition chamber. In this room, the 'precursor system infiltrates the surface of the wafer with ripe energy' and results in the following reaction formula: 2Cu (hfac) L—Cu ten Cu (hfac) 2 + 2L (reaction) Steel (C11) Deposited on the upper surface of the wafer, and there are Cu (hfaCh by-products. The gaseous Lewis-based by-products (2l) are excluded from the chamber. The appearance of by-products and other contaminants on the wafer surface reduces copper The adhesion to the lower diffusion barrier, such as nitride. In order to change the adhesion to the lower diffusion barrier, the process for depositing copper is divided into two steps. In the first step, the physical vapor phase The deposition (PVD) system is performed to deposit a copper seed layer 3 in pVD, a copper age system is placed on the substrate, and the above system is deposited for feeding. The gas system is introduced between the copper trunk and the substrate In the environment, argon gas is then excited through the use of radio frequency (rf) signals to create a plasma containing ions. The ions from the plasma collide with a copper target, which breaks down the steel particles and deposits them on the substrate. These copper particles are roughly ionized and are therefore high energy. To the barrier layer. The substrate is biased so that a voltage gradient is formed between the target and the substrate, thereby causing copper ions to accelerate the gradient and bombard the substrate. As a result of the bombardment, copper particles strongly adhere to the surface of the substrate. Second, this PVD process provides a clean interface between the copper seed layer and the barrier layer. Once the copper seed layer is deposited using PVD, a primary material copper layer is deposited. The primary material layer is made using standard chemistry It is deposited by vapor deposition or electroplating. The main material layer of copper adheres to the copper seed layer quite well. Page 5 This paper size applies to China National Standard (CNS) Λ4 specification (2 丨 OX297) 漦 ---- ---- ,, --- ^ ----, order ------ ^ * (Please read the precautions on the back 苒 fill out this page) 414813 A7 A B7 V. Description of the invention () However 'PVD The use of the process results in poor step coverage, which is unacceptable for devices with small characteristics. Furthermore, the PVD process cannot be completed in the same room as the chemical vapor deposition chamber or the bond. Because of the need for a PVD chamber and either CVD or Plating room 'while increasing integrated circuit manufacturing costs Therefore, I want to provide conformal chemical vapor deposition steel to the diffusion barrier layer, so that the adhesion between copper and the lower diffusion barrier layer can be improved. I also hope that this deposition can be performed in a single room ( Original position). I would like to reduce the generation of pollution by-products during copper deposition, so that the deposition can be carried out with a smaller amount of precursors and faster. Summary of the month 'According to the present invention, a layer of a material layer such as copper It is formed on the wafer surface in a modified manner. When forming a copper layer, a seed crystal is first formed on the surface of the wafer. Once the seed layer is deposited, the copper is bombarded (annealed) with ions to improve the copper's adhesion to the wafer surface. More specifically, the ions in the plasma of the inert gas bombarded the copper 'with adhesion, which caused the copper to be "mounted" on the surface of the wafer. This installs the adhesion of copper to the wafer surface. In addition, this bombardment flattens the copper and improves the mobility of the charge. The plasma system is produced in an embodiment of the present invention using an inert body 'such as argon. Alternatively, hydrogen can be used with a matching gas to generate a plasma that bombards copper, and the addition of pollutant exhaust provides the removal of copper by-products such as carbon, oxygen, fluorine, etc. to strengthen copper's barrier to Adhesion 3 ----- ------ ^ --- ^ ---- Order------ line (please read the precautions on the back before filling this page) Improved Chi Zhijing inertia removal. Printed by the Ministry of Economic Affairs, Intellectual Property, and Employee Consumer Cooperatives Page 6 (CNS) A4 specification (2 丨 0X297 public 414813 A7 B7 V. Description of the invention () Schematic illustration: Other details of the invention are Explained with the drawings, the figure: Figure 1 is a sequence of performing a copper layer deposition operation according to the present invention. Figures 2 (a) -2 (d) are a copper layer deposition according to the present invention. Figure 3 The illustration shows a copper deposition chamber according to the present invention = Fig. 4 is a control system for controlling the deposition chamber according to the present invention, which is used to deposit copper according to the present invention. Read the notes on the back and fill in ϊ: this page) Printed by the Intellectual Property of the Ministry of Economic Affairs and Industrial Cooperatives 110 Substrate 111 Insulating layer 1 12 Diffusion barrier layer 113 Seed layer 1 14 Plasma 115 Final copper layer 1 16 Vias 120 CVD system 12 1 gas panel 122 liquid panel 126 signal source 127 mixed block 128 evaporator 129 jet head 130 wafer support 13 1 wall surface 132 insulator 135 Force control unit 137 Processing chamber 140 Wafer 200 Control unit 205 Processor unit 2 1 0 Memory 220 Mass storage device 230 Heating element 250 Display unit 270 Input control early 7th paper size This paper applies Chinese National Standard (CNS) Λ4 Specification (2 ×× 297 mm) Intellectual property of the Ministry of Economic Affairs and employees “printed by Cooperative Cooperative 414813 A7 _ B7 V. Description of the invention () Detailed description of the invention: The first diagram illustrates the operation sequence of depositing copper on the wafer surface according to the present invention . First, in step 100, a seed layer is homogeneously deposited on a wafer. The surface 'seed copper' is deposited using a chemical vapor deposition method, and may be deposited as a continuous or discontinuous copper layer. According to the present invention, a Cu (hfac) L precursor system is used in the deposition of the seed layer. However, other copper precursors combined with reduction W] can be used to form a seed layer, such as Cu + 2 (hfac) L precursor and hydrogen reducing agent. Once the seed copper layer is deposited, in step 101, the seed layer is plasma treated. Plasma is generated by applying RF energy to one or more gases. In one embodiment of the present invention, the 'plasma gas contains only a single gas, such as argon, krypton, or xenon. In another embodiment of the invention, the gas mixture comprises a plurality of gases, such as a combination of argon and hydrogen, krypton and hydrogen, or xenon and gas. During plasma processing, a substrate that has been deposited with copper requires a bias voltage. The bias voltage causes the ions in the plasma to be accelerated toward the substrate. These ions impact copper, so that copper adheres to the surface of the substrate, that is, the copper crystal grains become M-mounted on the substrate, and at the same time, the crystal grains are planarized to improve the charge mobility. This enhances the adhesion of the copper seed layer to the substrate. At the same time, if hydrogen ions are present in the plasma, their combined precursors contaminate by-products and are removed from the chamber. Once the plasma treatment is completed in step 101, the steel deposition system of the main material is performed in step 102. When the main material is deposited, the deposited copper system is deposited on the plasma-treated copper to form a copper layer with a desired thickness and improved adhesion to the wafer surface. Use of the main material deposition system—Chemical Explosion, page 8 (Refer to CNS i Λ4 (Guangguang)) —---- T --- ^ ---- Installation ------ Order ----- -Line (please read the notes on the back before filling in ^: ^ page) 414813 at _ _ -__ Β7 V. Description of the invention () Vapor deposition is completed by Cu (hfac) L or other main material copper deposition. In one embodiment of the present invention, the copper seed layer deposition, the plasma treatment, and the main material deposition system are completed in a single chamber, and the chamber system can perform chemical vapor deposition and electrical mass processing. Therefore, the copper layer is completely formed in situ. In other embodiments of the present invention, the chemical vapor deposition and plasma processing systems are performed in different chambers. Figures 2 (a) -2 (d) illustrate the formation of a copper layer in a integrated circuit according to the present invention. Figure 2 (a) shows a through-hole 1 1 6 that has been formed (etched) in an insulating material (e.g., shredded dioxide) layer 1 1 1. The insulating material layer 11 is superposed on the substrate 110 ', which is capable of being electrically coupled to other components in the integrated circuit. The substrate 11 is connected to other components by an interconnect structure, which will be formed in the through hole 116. The upper surface of the material of the insulating layer 111 and the inner surface of the through hole 116 The upper surface of the substrate 110 is covered by a diffusion barrier layer π 2. The diffusion barrier layer π 2 is used to prevent the metal of the interconnect structure from diffusing into the substrate 110. In one embodiment of the present invention, the interconnect structure metal is copper, and the diffusion barrier layer is a refractory metal or a refractory metal nitride. For example, the refractory metal nitride is preferably tantalum nitride, but it can also be a titanium nitride 'button, nitride nitride, or other suitable materials for the diffusion barrier layer between the metal (such as copper) and the substrate 110. Figure 2 (b) illustrates the deposition of a copper seed layer 1 13 which can be used in an interconnect structure. The copper seed layer 11 3 is deposited on the upper surface of the diffusion barrier layer 112 by a chemical vapor deposition method. In one embodiment of the present invention, the __th paper standard is applicable to the standard Tcns) Λ4 specification (~ — A Please read the notes on the back 0 before filling out this page. Installation · Ministry of Economic Affairs Intellectual Property 笱 33 > 'Industrial and Consumer Cooperatives' Seal 414813 A7 B7 V. Description of the Invention () As shown in Figure 2 (b), the copper seed layer 1 13 is deposited discontinuously, that is, there is a gap between the deposition areas. In the embodiment (not shown), the copper seed layer 11 3 is successively deposited to a thickness ranging from 100 angstroms to 300 angstroms. The thickness of the seed layer depends on the electricity used to process the seed layer. Slurry processing parameters. Therefore, the thickness of the deposition should match the selected processing parameters. The chemical vapor deposition of the seed layer 1 Π is preferably completed using a Cu (hfac) L front plate, L is VTMS. Liquid Cu (hfac L) is vaporized and flows into the environment containing the diffusion barrier layer 112. The vaporization of the precursor can be accomplished by "foaming through the precursor 11" nitrogen or hydrogen. The vaporized precursor system is A velocity of flow to 1 seem is provided to the environment. The environment is controlled so that it has a range of 0-5 mTorr. A pressure of 5 mTorr, and the substrate is in a temperature range of 150 ° C to 250 ° C. The deposition process is performed in a period of time ranging from 30 seconds to 5 minutes. The desired thickness of the seed layer. The seed layer can use other copper precursors, such as

Cu + 2(hfach及氫還原劑加以化學沉積。廣泛地說，任何形 式之銅沉積係被考慮於本發明之範圍中。 一旦晶種銅層1 1 3被沉積，則其被以—電漿丨1 4所處 理’如於第2(c)圖所示。依據本發明’電漿1 1 4係被藉由 提供能量至一或多數氣體’即一氣體混合物中加以形成， 該氣體混合物包含一惰性氣體，具有一原子質量類似於銅 \ 之原子質量。此氣體包含氬，氙及氪。於本發明之—實施 例中，氣體混合物包含氬。 當風被使用時’一風氣係被以100至500sccm之流速 範圍流入含晶種銅層11 3之環境中。氬氣體係藉由將其灌 %紙張尺度適用;國國家標準（〔：^)..\4規格（2丨0乂29了公楚） 請先閱讀背面之注意事項再填寫太頁) 訂 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印" 414813 A7 ^^ ___B7 五、發明説明（） 入以來自圍100kHZ-20MHZ之RF信號之能量，而被轉換 為電漿，其中13.56MHZ使用100瓦至2〇〇〇瓦範圍之RF 功率位準已經被發現產生足夠處理結果。一般說來，施加 至電漿之功率愈尚’則晶種層之處理愈好。所得電漿丨玉4 係被維持範圍1 0至6 0秒之時間段。 當執行電漿處理時’晶種銅層1 1 3之環境係被控制， 使得壓力是於範圍0.1至1.5托耳，及基板110之溫度係 被設定於150至250°C之範圍中。 當電漿1 1 4被形成時，氬變成離子化。所得氬離子加 速向晶種鋼層並衝擊向銅層Π3。來自離子之衝擊使得被 衝擊之銅層U4具有對擴散阻障層Π2之改良結合。銅材 料之此”安裝"於擴散阻障層11 2改良了銅晶種層11 3對擴 散阻障層1 1 2上之附著力。 於本發明之另一實施例中，電漿Π 4係被由_氣體混 合物中形成’該混合物係氫與惰性氣體’例如氬，氪或氙 之混合物°當氬被使用時，氬對氫之比例是於範圍1:1 至；3 : 1之範圍中。電漿係由氬及氫之氣體混合物所形成， 這係藉由以相同於形成只有氬之電漿之方式，提供能量至 氣體中。 如上所述’使用Cu(hfac)L前驅物之銅之化學氣相沉 t 積法造成了銅沉積時，與:¾染（hfac)副產物之產生。污染 副產物負面影響了銅113之附著裘擴散阻障層112上。氬 之加至電漿Π4中造成了（hfac)副產物之一部份，及其他 污染物，例如氟，氧，及/或碳之減少。 ______第11 頁__________ ^紙張尺度適用中國國家標準（CNS ) Λ4規樁（210X 297公釐） ----_---；----農------訂------線 - - {請先閱讀背面之注意事項再填衿本買〕 經濟部智惡財產苟具工消費合作社印契 414813 A 7 B7 五、發明説明（） 當氬-氫電漿1 14被使用時’氬離子如上述地衝擊銅 11 3，及氫依據下式组合（hfac)副產物： H2 + (hfac).....2H(hfac) (反應式 2) 2H(hfac)是反應之氣體副產物，並被由晶種層丨丨3被 沉積之環境中排出。因為使用氬氫電漿1 1 4之結果，所以， 晶種層1 1 3之附著至擴散阻障層1 1 2係被兩機制所改良。 第一機制是以氬離子爲擊销而改良於_及擴散阻障層1 ^ 2 問之結合。第二機制是將結合氫（hfac)污染副產物及/或其 他污染物之消除，並被由該等室中除去。 於本發明之其他實施例中’電漿1 1 4可以被變化，同 時完成於銅晶種層1 1 3及下層擴散阻障層11 2間之附著 力。例如’其他惰性氣體，例如氪及氙可以替代於電漿1 i 4 中之氬。這些替換可以在使用氫或不使用氫之情形下加以 完成。再者’電漿1 1 4可以只以氳構成。於此一實施例中， 於銅晶種層1 1 3及擴散阻障層1 1 2間之改良附著力，係由 (hfac)副產物及其他可能干擾銅結合之污染物之消除而完 成。 一旦晶種銅層1 1 3係被以電漿11 4處理，一主材質沉 積銅係被執行以形成具有想要厚度之最終銅層115。如於 第2(d)圖所示，新沉積之銅係被使用化學氣相沉積加以沉 積，並與铜1丨3晶種層一起出現（成長），以形成最終之銅 層Π 5。於本發明之較佳實施例中，主材質CVD铜層1 J 5 係參考第2(b)圖，使用Cu(hfac)L前驅物加以形成；然而， 其他主材質沉積處理可以使用，例如CU + 2(hfac)2與氫還 _ 第12頁 本紙蒗尺度適用中國3家標準（CNS ) A4規格（210X 297公釐） ---^---；----裴，—-----1T------,線 > (請先閱讀背面之注意事項再填鸿本頁) 414813 A7 B7 五、 經濟部智慧財凌局資'工消費合作钍印說 發明説明（ 原劑。 主材質銅之沉積係被完成直到銅之最終層ii5具有 100-埃至1微米之厚度為止。因為新沉積銅是沉積於對下 層擴散阻障層112具有改反附著力之晶種層113之上所 以最終㈣U5對擴散阻障I 112之附著力同時也被改 良，於研磨時，銅較不會被由擴散阻 第3圖例一物，其可以使用以J:依據本 發明之铜層。該室係為由美國加州聖塔卡拉之應用材料公 司所製造之模型WxZ室，其已經被修改以執;依據本^ 明之銅沉積。系統120包含一處理室137，其中執行銅沉 積及電衆處理。包含於處理室丨37中的是一晶圓支撐 Π 0 ’用以支持晶圓及一噴氣頭1 29，用以使反應氣體流入 處理室1 3 7中。 處理至1 3 7係被一組壁面1 3 1所定義，並被絕緣器1 3 2 所電氣及熱阻隔開晶圓支撐130及噴氣頭129。為了提供 熱能，晶圓支撐1 3 0包含一阻抗線圈（未示出），其提供熱 至晶圓支撐面上。為了提供形成電漿：之能量，喷氣頭129 係連接至一信號源1 26，其提供具有頻率範園丨ookHz至 20MHz之信號。處理室壁131及晶圓支撐130均係接地。 一壓力控制單元1 3 5，例如真空泵，係連接至處理室 137，用以設定於處理室137中之壓力。壓力控制單元135 同時提供以由處理室排除反應副產物。 為了提供反應物至處理室137’系統120同時包含一 混合方塊127，蒸發器128，氣體面板121，及液體面板 第13頁 本紙展尺度適用中國國家標隼（CNS ) Λ4规格（2U)X297公t ) --------.------ic------IT------ I * t請先閱讀背面之注意事項再填"木頁) 經濟部智慧財麦苟員工"費合作钍印製 414B13 A? B7 五、發明説明（） 122。氣體面板121提供氣體反應物並連接至蒸發器128 與混合方塊1 27。液體面板1 22提供液體反應物並連接至 蒸發器128。 蒸發器128提供用以轉換液體反應物成為氣體反應 物。當一液體反應物被使用時，液體面板122提供液體反 應物至蒸發器128 ’蒸發器128蒸發液體並使用一惰性稀 釋氣體，例如氦，氫，氮或氬作為載氣。或者，蒸發器可 以經由汽化產生氣體反應物。當氣體及液體反應物被使用 時’氣體面121提供氣體反應物給蒸發器128，及液體面 板1 2 2提供液體反應物給蒸發器丨2 8。蒸發器然後提供這 些反應物I组合與汽化。混合方塊i 2 7係連接，以由氣體 面板121及義發器128傳送氣體反應物至喷氣頭ι29。 銅層之形成係被原處執行於如第3圖中所示之單一處 理系統中》—包含上表面沉積有銅之晶圓丨4〇係被放置於 處理室137之晶圓支撐13〇上，支撐係離開喷氣頭129約 」：>〇密耳。^本發明之—實施例中，晶圓i4Q之上表面是 擴散阻障^其係藉由耐火金屬氮化物，例如氮化鈦， 亂化鈕，或氮化鎢形成。晶圓（基板）係然後被如上所處理。 上述用以形成銅層之處理步驟（第2(a)至2(d)圖）可以 幸’亍於系光中該系统係由處理機為主控制單元所控 制。第 4 圖出一 Jife ^|j 62 —— 控制革兀2 Ο Ο ’其可以用於此一設備中。 控制單元包含-處理機單元2〇5，一記憶體21〇，—大量 儲存裝jl 220 ~輸入控制單元，及一顯示單元， 其均是連接至一控制單元匯流排225。 ----*---：---I 次------訂 I 1 1 線 > - -請先閱讀背面之注意事項再填寫本頁) 本紙ft尺度it财關^:鮮 第14頁 (2!CU'297公釐 敏濟部智慧財產局S工消費合作社印製 414813 A7 --- B7 五、發明説明（） 處理機單元205不是一微處理機就是其他引擎，其係 能執行儲存於一記憶體中之指令者。記憶體2 1 0可以包含 硬碟機’隨機存取記憶體（RAM)，唯讀記憶體（ROM)，RAM 及ROM之组合’或者其他處理機可讀取儲存媒體。記憶 體210包含處理機單元2〇5執行以完成上述處理步驟效能 之指令。於記憶體2〗〇中之指令係以程式碼之形式。程式 碼可以配合若干不同程式語言之一種。例如，程式碼可以 被寫成C+，C + +，培基，巴斯卡，或其他語言。 大量儲存裝置2 2 0儲存資料及指令，並由一例如磁碟 機或磁帶之處理機可讀取儲存媒體中取回資料及程式碼 指令。例如，大量儲存裝置22〇可以是一硬碟機，軟碟機， 磁帶機’或光碟機。大量儲存裝置22〇反應於其由處理機 單兀205所接收之指示’而儲存並取回指令。由大量儲存 裝置220所儲存及取回之資料及程式碼指令係被處理機單 元2 0 5所使用，以執行上述之步驟。資料及程式碼指令係 首先被大量儲存裝置2 20所由媒體取回，然後，被傳送給 記憶體2 1 0 ’為處理機單元2 〇 5所使用。 顯示單元250在處理機單元205之控制下，以圖像顯 示及數目文字之形式，提供資訊給一室操作者。輸入控制 單元270連接一資料輸入裝置，例如一鍵盤，滑鼠或光筆， 以控制單元200，用以接收室操作者之輸入。 控制單元匯流排225用以傳送資料及控制信號於這些 連接至控制單元匯流排2 2 5之裝置之間。雖然，控制單元 匯流排係被顯示為單匯流排，其直接連接裝置於控制單元 ______第15百_ 本紙乐尺度適用中國國家標準（CN’S ) Λ·4規格（210X 297公犛) ' ~ ----；---：---"------訂--------線 > - Γ請先閲讀背面之注意事項再填寫本頁〕 414813 A7 B7 五、發明説明（ 200中’但是該控制單元匯流排225可以是匯流排之集 合。例如’顯示單元250，輸入控制單元27〇，及大量儲 存裝置220可以連接至輸入_輸出週邊匯流排’而處理機 單元205及記憶體2 1 〇可以連接至一區域處理機匯流排。 區域處理機匯流排及輸入-輸出週邊匯流排係連接在一 起’以形成控制單元匯流排2 2 5。 控制單元220係連接至於第3圖中之室之各元件’其 係用以依據本發明形成一鋼層。這些元件均連接至控制單 元匯流排225，以使控制單元22〇及元件間之通訊容易。 這些元件包含以下：氣體面板i2i，液體面板122 ’一加 熱元件230，例如阻抗線圈（未示出）於晶圓支撐中，壓力 控制單兀1 3 5 ’信號源126，蒸發器】2 8及混合方塊！ 27。 控制單元200提供信號給室元件’這使得元件執行上述之 操作，以用於用以形成銅層之處理步驟中。 於操作中，處理單元205反應於來自記憶體210取回 (式碼指令’而指示室元件之操作。反應於這些指令， 至兀*件係被指示以執行上述參考第丨圖之處理步驟。 一旦晶圓被故於處理室中，一晶種銅層係於步驟100 中仉積晶圓上(第i圖）。& 了於步驟⑽中執行沉積，處 理機單元205執行由記憶體21〇取回之指令。這些指令之 執行造成了室元件被操作以沉積_層材料於—基板上，如 上述參考第2(b)圖所描述。 旦阳種鋼層被沉積時’由記憶體2丨〇取回之指令指 示處理機單it 2〇5，以使得室m之元件於步驟1〇2中執 請先閱讀背面之注意事項再填寫本頁 .装. 訂 經濟部智慧財產苟53:工消費合作社印製Cu + 2 (hfach and hydrogen reducing agent are chemically deposited. Broadly speaking, any form of copper deposition is considered within the scope of the present invention. Once the seed copper layer 1 1 3 is deposited, it is used as a plasma丨 14 treated 'is shown in Figure 2 (c). According to the present invention,' plasma 1 1 4 is formed by supplying energy to one or most gases', that is, a gas mixture, the gas mixture contains An inert gas with an atomic mass similar to that of copper. This gas contains argon, xenon, and krypton. In the embodiment of the present invention, the gas mixture contains argon. When the wind is used, a wind gas system is used The flow rate range of 100 to 500 sccm flows into the environment containing the seed copper layer 113. The argon system is applied by filling it with% paper size; national national standards ([: ^) .. \ 4 specifications (2 丨 0 乂 29 Please read the notes on the back before filling in the page.) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives of the Ministry of Economic Affairs. Printed by the Ministry of Economic Affairs and the Intellectual Property Bureau of the Employees ’Consumer Cooperatives. &Quot; 414813 A7 ^^ ___B7 RF signal from around 100kHZ-20MHZ Energy, is converted into a plasma, wherein the RF power level used 13.56MHZ watts to 100 watts of 2〇〇〇 has been found to produce sufficient processing results. Generally speaking, the more the power applied to the plasma ', the better the treatment of the seed layer. The resulting plasma 丨 jade 4 is maintained for a period of time ranging from 10 to 60 seconds. When the plasma treatment is performed, the environment of the 'seed copper layer 1 1 3 is controlled so that the pressure is in the range of 0.1 to 1.5 Torr, and the temperature of the substrate 110 is set in the range of 150 to 250 ° C. When the plasma 1 1 4 is formed, argon becomes ionized. The resulting argon ions accelerate toward the seed steel layer and impinge on the copper layer Π3. The impact from the ions gives the impacted copper layer U4 an improved combination of the diffusion barrier layer Π2. The "installation of copper material" on the diffusion barrier layer 11 2 improves the adhesion of the copper seed layer 11 3 to the diffusion barrier layer 1 12. In another embodiment of the present invention, the plasma Π 4 The system is formed from a gas mixture 'the mixture is a mixture of hydrogen and an inert gas' such as a mixture of argon, krypton, or xenon. When argon is used, the ratio of argon to hydrogen is in the range of 1: 1 to 3: 1. Medium. Plasma is formed from a gas mixture of argon and hydrogen, which provides energy to the gas in the same way as a plasma with only argon. As described above, 'Using Cu (hfac) L precursor The chemical vapor deposition method of copper caused the formation of copper by-products during the deposition of copper. The pollution by-products negatively affected the adhesion of copper 113 to the diffusion barrier layer 112. The addition of argon to the electricity A part of (hfac) by-products and other pollutants, such as fluorine, oxygen, and / or carbon reduction in pulp Π4. ______ page 11 __________ ^ Paper size applies Chinese National Standard (CNS) Λ4 Gauge Pile (210X 297mm) ----_---; ---- Agriculture ------ Order ------ Line--{Please read the back Note for re-filling the purchase]] Intellectual property of the Ministry of Economic Affairs and the Industrial and Commercial Consumers' Cooperative Seal 414813 A 7 B7 V. Description of the invention () When the argon-hydrogen plasma 1 14 is used, argon ions impact copper as described above 11 3, and hydrogen according to the following formula (hfac) by-product combination: H2 + (hfac) ..... 2H (hfac) (Reaction formula 2) 2H (hfac) is the reaction gas by-product and is controlled by the seed layer丨 丨 3 is discharged from the deposited environment. As a result of using the argon-hydrogen plasma 1 1 4, the adhesion of the seed layer 1 1 3 to the diffusion barrier layer 1 1 2 is improved by two mechanisms. The first mechanism The combination of argon ions as a knock-off and improvement of diffusion barrier layer 1 ^ 2 question. The second mechanism is the elimination of combined hydrogen (hfac) pollution by-products and / or other pollutants, and is eliminated by these Removed in the chamber. In other embodiments of the present invention, the 'plasma 1 1 4 can be changed and the adhesion between the copper seed layer 1 13 and the lower diffusion barrier layer 112 can be completed at the same time. For example,' other inert gas' For example, krypton and xenon can be substituted for argon in plasma 1 i 4. These substitutions can be done with or without hydrogen. . Furthermore, the 'plasma 1 1 4 may be composed only of osmium. In this embodiment, the improved adhesion between the copper seed layer 1 13 and the diffusion barrier layer 1 12 is caused by (hfac) The elimination of products and other contaminants that may interfere with copper binding is completed. Once the seed copper layer 1 1 3 is treated with plasma 11 4, a master material deposition copper system is performed to form the final copper layer with the desired thickness. 115. As shown in Fig. 2 (d), the newly deposited copper system is deposited using chemical vapor deposition and appears (growth) with the copper 1 丨 3 seed layer to form the final copper layer Π 5 . In a preferred embodiment of the present invention, the main material CVD copper layer 1 J 5 is formed by using Cu (hfac) L precursors with reference to FIG. 2 (b); however, other main material deposition processes can be used, such as CU + 2 (hfac) 2 and hydrogen reduction_ Page 12 The paper scale is applicable to three Chinese standards (CNS) A4 specifications (210X 297 mm) --- ^ ---; ---- Pei, ----- --1T ------, line > (Please read the notes on the back before filling in this page) 414813 A7 B7 V. The "Industrial and Consumer Cooperation Cooperation Seal" of the Ministry of Economic Affairs and the Intelligent Finance Bureau said the invention description (Originally The main material copper deposition is completed until the final copper layer ii5 has a thickness of 100-Angstroms to 1 micron. Because the newly deposited copper is deposited on the seed layer that has a reverse adhesion to the underlying diffusion barrier layer 112 Above 113, the adhesion of U5 to diffusion barrier I 112 is also improved at the same time. During grinding, copper is less likely to be affected by diffusion resistance. Figure 3 can be used. J: The copper layer according to the present invention can be used. The room is a model WxZ room manufactured by Applied Materials, Inc. of Santa Cala, California, United States, which has been modified to comply; The system 120 includes a processing chamber 137, which performs copper deposition and electrical processing. Included in the processing chamber 37 is a wafer support Π 0 'to support the wafer and a jet head 129 to enable The reaction gas flows into the processing chamber 1 3 7. The processing to 1 3 7 series is defined by a set of wall surfaces 1 3 1 and is electrically and thermally separated by the insulator 1 3 2 to separate the wafer support 130 and the air jet head 129. In order to provide Thermal energy, the wafer support 130 includes an impedance coil (not shown), which provides heat to the wafer support surface. In order to provide plasma forming energy, the air-jet head 129 is connected to a signal source 126, which Provides signals with frequency range from ookHz to 20MHz. The processing chamber wall 131 and wafer support 130 are grounded. A pressure control unit 1 35, such as a vacuum pump, is connected to the processing chamber 137 for setting in the processing chamber 137. The pressure control unit 135 is also provided to exclude reaction by-products from the processing chamber. In order to provide reactants to the processing chamber 137 'the system 120 also includes a mixing block 127, an evaporator 128, a gas panel 121, and a liquid panel 13 Sheet paper ruler Applicable to China National Standard (CNS) Λ4 specification (2U) X297 male t) --------.------ ic ------ IT ------ I * t Please First read the notes on the back and fill in the "Wood Pages" employees of the Ministry of Economic Affairs, Smart Financial Maigo, and printed 414B13 A? B7 V. Description of the invention () 122. The gas panel 121 provides a gas reactant and is connected to the evaporator 128 and the mixing block 127. The liquid panel 122 provides liquid reactants and is connected to the evaporator 128. The evaporator 128 is provided to convert liquid reactants to gaseous reactants. When a liquid reactant is used, the liquid panel 122 provides the liquid reactant to the evaporator 128 '. The evaporator 128 evaporates the liquid and uses an inert diluent gas such as helium, hydrogen, nitrogen, or argon as a carrier gas. Alternatively, the evaporator may generate gaseous reactants via vaporization. When gas and liquid reactants are used, the 'gas surface 121 provides gas reactants to the evaporator 128, and the liquid panel 1 2 2 provides liquid reactants to the evaporator 218. The evaporator then provides these reactants I in combination with vaporization. The mixing block i 2 7 is connected to transfer the gas reactants from the gas panel 121 and the transponder 128 to the jet head 29. The formation of the copper layer is performed in situ in a single processing system as shown in Fig. 3—a wafer containing copper deposited on the upper surface. The 40 is placed on the wafer support 13 of the processing chamber 137. , The support is about 129 from the jet head ": > 0 mil. ^ In the embodiment of the present invention, the upper surface of the wafer i4Q is a diffusion barrier. ^ It is formed by a refractory metal nitride, such as titanium nitride, a chaotic button, or tungsten nitride. The wafer (substrate) is then processed as above. The above-mentioned processing steps for forming a copper layer (FIGS. 2 (a) to 2 (d)) can be used in the system, which is controlled by the processor as the main control unit. Figure 4 shows a Jife ^ | j 62 —— control leather 2 〇 Ο ’which can be used in this device. The control unit includes a processor unit 205, a memory 21, and a large number of storage jl 220 ~ input control units, and a display unit, all of which are connected to a control unit bus 225. ---- * ---: --- I times ------ Order I 1 1 line >--Please read the precautions on the back before filling in this page) ft scale it finances ^: Fresh Page 14 (2! CU'297 mm printed by Minji Ministry of Intellectual Property Bureau, S Industrial Consumer Cooperative, 414813 A7 --- B7 V. Description of the invention () The processor unit 205 is either a microprocessor or other engine. Those who can execute instructions stored in a memory. Memory 2 1 0 can include a hard disk drive 'random access memory (RAM), read-only memory (ROM), a combination of RAM and ROM', or other processors Readable storage medium. Memory 210 contains instructions executed by processor unit 205 to complete the performance of the above processing steps. The instructions in memory 2 are in the form of code. The code can cooperate with several different programming languages One. For example, the code can be written in C +, C ++, Peckey, Baska, or other languages. Mass storage device 2 2 0 stores data and instructions and is processed by a processor such as a disk drive or magnetic tape Can read data and code instructions from storage media. For example, mass storage devices 22 It is a hard disk drive, floppy disk drive, tape drive 'or optical drive. The mass storage device 22 stores and retrieves instructions in response to instructions received by the processing unit 205. The mass storage device 220 stores And retrieved data and code instructions are used by the processor unit 205 to perform the above steps. The data and code instructions are first retrieved by the mass storage device 2 20 from the media, and then transmitted to The memory 2 1 0 'is used by the processor unit 2 05. The display unit 250 provides information to the operator of the one room in the form of image display and numerical characters under the control of the processor unit 205. The input control unit 270 Connect a data input device, such as a keyboard, mouse or light pen, to the control unit 200 to receive input from the operator of the room. The control unit bus 225 is used to transmit data and control signals to the control unit bus 2 Between 2 and 5 devices. Although the control unit bus is shown as a single bus, it is directly connected to the control unit ______150th_ This paper music scale is applicable to the country of China Standard (CN'S) Λ · 4 specification (210X 297 cm) '~ ----; ---: --- " ------ order -------- line>-Γ Please read the notes on the back before filling in this page] 414813 A7 B7 V. Description of the invention (200) But the control unit bus 225 can be a collection of buses. For example, 'display unit 250, input control unit 27, and The mass storage device 220 can be connected to the input-output peripheral bus' and the processor unit 205 and the memory 2 10 can be connected to a regional processor bus. The area processor bus and the input-output peripheral bus are connected together 'to form a control unit bus 2 2 5. The control unit 220 is connected to the elements' of the chamber in Fig. 3 and is used to form a steel layer according to the present invention. These components are connected to the control unit bus 225 to facilitate communication between the control unit 22 and the components. These components include the following: gas panel i2i, liquid panel 122 'a heating element 230, such as an impedance coil (not shown) in a wafer support, pressure control unit 1 3 5' signal source 126, evaporator] 2 8 and Mixed blocks! 27. The control unit 200 provides a signal to the chamber element 'which causes the element to perform the operations described above for use in a processing step for forming a copper layer. In operation, the processing unit 205 instructs the operation of the room element in response to the retrieval of the (code instruction) from the memory 210. In response to these instructions, the components are instructed to perform the processing steps described above with reference to FIG. Once the wafer is left in the processing chamber, a seed copper layer is deposited on the wafer deposited in step 100 (figure i). &Amp; In order to perform the deposition in step 2, the processor unit 205 executes the fetch from the memory 21 Back to the instructions. The execution of these instructions caused the chamber elements to be operated to deposit the layer material on the substrate, as described above with reference to Figure 2 (b). When the Danyang seed steel layer is deposited, 'from the memory 2 丨〇The instruction to retrieve instructs the processor to order it 20.5, so that the components of the room m are executed in step 102. Please read the precautions on the back before filling in this page. Printed by a cooperative

414813 A7 B7 五、發明説明（） 行電漿處理。這些指令之執行造成了室之元件 120被操 作，以電漿來處理沉積銅，如同上述參考第2(c)圖所述者。 一旦電漿處理完成時，由記憶體2 1 0所取回之指令指 示處理機單元205，以使得室1 20之元件執行主材質銅沉 積於步驟1 0 2中。這些指令之執行造成室1 2 0之元件中被 操作，以執行一主材質沉積，以如上述參考第2(d)圖所述 地處理銅。 雖然本發明已經以特定例示性實施例加以說明，但可 以了解的是各種修改及替換，可以在不脫離由以下之申請 專利範圍所指定之本發明之精神及範圍下，為熟習於本技 藝者所完成。 (請先閱讀背面之注意事項再填寫本頁 装 訂 線 經濟部智慧財產局員工消費合作社印製 第17頁 本紙乐尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐）414813 A7 B7 V. Description of the invention () Plasma treatment. Execution of these instructions caused the element 120 of the chamber to be operated to treat the deposited copper with a plasma, as described above with reference to Figure 2 (c). Once the plasma processing is completed, the instruction retrieved by the memory 2 10 instructs the processor unit 205 so that the components of the chamber 120 perform the main material copper deposition in step 102. Execution of these instructions causes the components in chamber 120 to be manipulated to perform a master material deposition to process copper as described above with reference to Figure 2 (d). Although the present invention has been described with specific exemplary embodiments, it can be understood that various modifications and substitutions can be made by those skilled in the art without departing from the spirit and scope of the present invention specified by the following patent application scope. Completed. (Please read the notes on the back before filling in this page. Binding Line Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Page 17 The paper scale is applicable to the Chinese National Standard (CNS) Λ4 specification (210X297 mm)

Claims (1)

3 '上 8 4 ".丄 4 ABC0 申1青幸利範圍 1 · 一種用以改良銅附著至基板之方法，至少包含下列步 驟： (a) 沉積銅於基板上；及 (b) 經由離子轟擊，而處理銅，以使得銅附著至基板 之上表面。 2 .如申請專利範圍第1項所述之方法，其中上述之步驟（b) 包含步騾： 形成一電漿，其中電漿包含離子，其轟擊銅。 3. 如申請專利範圍第1項所述之方法，其中上述之銅是沉 積於一連續層中。 4. 如申請專利範圍第1項所述之方法，其中上述之銅是沉 積於一不連績層中。 5. 如申請專利範圍第1項所述之方法，其中上述之基板包 含一擴散阻障層。 6. 如申請專利範圍第5項所述之方法，其中上述之擴散阻 障層包含一耐火金屬或耐火金屬氮化物。 7. 如申請專利範圍第6項所述之方法，其中上述之擴散阻 障層是一材料，其係由包含輕，氮化鈥，氮化纽及氮化 第18頁 本紙法尺度適用中國國家橾準（CNS ) A4規格（210乂297公釐） ---,---..----^------訂--------線 - f ~請先閲讀背面之注意事"再填芎衣頁) 經濟部中央標準局員工消費合作社印製 ABCD 414813 六、申請專利範圍 鎢之群組中選出。 (請先閱讀背面之注意事項再填窝·"頁) 8. 如申請專利範圍第2項所述之方法，其中上述之電漿係 使用一惰性氣體形成。 9. 如申請專利範圍第8項所述之方法，其中上述之惰性氣 體具有一原子質量接近配合銅之原子質量。 1 0.如中請專利範圍第9項所述之方法，其中上述之惰性氣 體是一或多數氣體，其係由包含氬，氪及氙之群組中選 出。 1 1.如申請專利範圍第8項所述之方法，其中上述之惰性氣 體係組合以氫。 1 2.如申請專利範圍第1項所述之方法，更包含步驟： (c)沉積銅於步驟（a)中所沉積並處理於步驟（b)之銅 上。 經濟部中央標準局員工消費合作社印製 1 3 .如申請專利範圍第1 2項所述之方法，其中上述之沉積 1 於步騾（C)中之銅組合以沉積於步驟（a)之銅，以形成一連 續之銅層。 1 4 .如申請專利範圍第1 3項所述之方法*其中上述之步驟 第19頁 本紙張尺度適用中國國家橾準（CNS > A4規格（210X297公嫠） 414813 ABCD 經濟部中央標準局員工消費合作.社印製 六、申請專利範圍 (a)，（b)，（c)均執行於一處理室中，及晶圓並未由該處 理室中移開，直到步驟（a)，（b)及（c)完成為止。 1 5.如申請專利範圍第1項所述之方法，其中上述之步驟（a) 是使用化學氣相沉積法加以執行。 1 6.如申請專利範圍第1 5 J員所述之方法，其中上述之化學 氣相沉積法係使用Cu(hfac)L化學化合物加以完成。 17.—種用以於晶圓上之材料層上形成一銅層之方法，該方 法至少包含下列步驟： (a) 放置晶圓於一處理室中； (b) 當晶圓於處理室之同時，化學氣相沉積銅於該材 料層上；及 (c) 當晶圓於處理室之同時，處理銅，使得銅附著至 材料層之上表面。 1 8 ·如申請專利範圍第1 7項所述之方法，其中上述之步騾 (c)包含步驟： 形成一電漿，其中該電漿包含衝擊該銅之離子。 1 9.如申專利範圍第1 7項所述之方法，其中上述之材料層 是一擴散阻障層。 第20頁 本紙張尺度適用中國國家標準（CNS ) A4规格（UOX297公釐） i- _二 I -女.尺〆 — -I I pup— - 1 - I ^1^11 - -I -丨 _(請先閱讀背面之注意事項再填巧本頁) 4' j_4⑽ A8 B8 C8 D8 經濟部中央標隼局員工消費合作社印製 ττ、申請專利範圍 20.如申專利範圍第1 7項所述之方法，其中上述之電漿係 使用包含惰性氣體之氣體混合物形成。 2 1.如申專利範圍第20項所述之方法，其中上述之惰性氣 體具有接近配合於銅原子質量之原子質量。 2 2 .如申專利範圍第2 0項所述之方法，其中上述之惰性氣 體是一氣體，其係由包含氬，氪及氙群組之中選出。 23 .如申專利範圍第20項所述之方法，其中上述之氣體混 合物包含至少一氣體，其係由包含氬，氪，氙及氫群组 所選出。 24.如申專利範圍第1 7項所述之方法，更包含步驟： (d)當晶圊於處理室之同時，沉積銅於步驟（b)所沉積 之銅上。 25 .如申專利範圍第24項所述之方法，其中上述之步驟（d) 是使用化學氣相沉積法加以執行。 26. 如申專利範圍第25項所述之方法，其中上述之化學氣 相沉積是使用Cu(hfac)L化學化合物加以完成。 27. —種包含一程式之電腦可讀取媒體，用以於一半導體晶 第21頁 本紙張尺度適用中國國家榡準（CNS ) Λ4規格（210X2M公釐） (緣先閱讀背面之注意事巧'再"寫本頁 裝- 線 經濟部中夬標隼局員工消費合作社印製 414813 g C8 D8六、申請專利範圍 圓處理系統中，該系統包含執行化學氣相沉積之一室及 用以控制於該室内之化學氣相沉積之電腦，當該程式為 電腦所執行時，使得該半導體晶圓處理系統系統執行以 下步驟： 沉積一銅晶種層於一基板上； 供給處理氣體至該室； 激勵處理氣體成為一電漿，以離子轟擊該銅晶種 層。 2 8 .如申請專利範圍第2 7項所述之電腦可讀取媒體，更包 含一程式，其當被電腦所執行時，使得半導體晶圓處理 系統，執行以下步驟： 沉積一銅層於銅晶種層上。 2 9.如申請專利範圍第2項所述之方法，其中電漿係使用氫 形成。 3 0 .如申請專利範圍第1 8項所述之方法，其中電漿係使用 氫形成。 (請先閱讀背面之注惠事項再填穹本頁 *" 線 第22頁 本紙張尺度適用中國國家揉準（CNS ) Α·4規格（210X29?公釐）3 '上 8 4 ". 丄 4 ABC0 Shen1 Qingxingli Scope1 · A method for improving the adhesion of copper to a substrate, including at least the following steps: (a) depositing copper on the substrate; and (b) by ion bombardment And copper is processed so that the copper adheres to the upper surface of the substrate. 2. The method according to item 1 of the scope of patent application, wherein step (b) above comprises the step of: forming a plasma, wherein the plasma contains ions that bombard copper. 3. The method according to item 1 of the scope of patent application, wherein the above-mentioned copper is deposited in a continuous layer. 4. The method described in item 1 of the scope of patent application, in which the above copper is deposited in a continuous layer. 5. The method according to item 1 of the scope of the patent application, wherein the above-mentioned substrate includes a diffusion barrier layer. 6. The method according to item 5 of the scope of patent application, wherein the diffusion barrier layer comprises a refractory metal or a refractory metal nitride. 7. The method as described in item 6 of the scope of patent application, wherein the above diffusion barrier layer is a material consisting of light, nitrided, nitrided, and nitrided pages. The paper method is applicable to China. Standard (CNS) A4 (210 乂 297mm) ---, ---..------------ Order -------- line-f ~ Please read first Note on the back " refill the page of clothing) Printed by ABCD 414813, Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. (Please read the precautions on the back before filling the "" page") 8. The method described in item 2 of the scope of patent application, wherein the above plasma is formed using an inert gas. 9. The method according to item 8 of the scope of patent application, wherein the above inert gas has an atomic mass close to that of copper. 10. The method as described in item 9 of the patent scope, wherein the above inert gas is one or more of gases selected from the group consisting of argon, krypton, and xenon. 1 1. The method according to item 8 of the scope of patent application, wherein the above inert gas system is combined with hydrogen. 1 2. The method according to item 1 of the scope of patent application, further comprising the step of: (c) depositing copper deposited in step (a) and processing on the copper of step (b). Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 13. The method described in item 12 of the scope of patent application, wherein the above-mentioned deposit 1 is a combination of copper in step (C) to deposit the copper in step (a) To form a continuous copper layer. 1 4. The method as described in item 13 of the scope of patent application * Among the above steps, page 19 This paper size applies to the Chinese National Standard (CNS > A4 size (210X297)) 414813 ABCD Employees of the Central Standards Bureau of the Ministry of Economic Affairs Consumption cooperation. Printed by the society 6. The scope of patent applications (a), (b), (c) are all implemented in a processing chamber, and the wafer is not removed from the processing chamber until step (a), b) and (c) until completion. 1 5. The method described in item 1 of the scope of patent application, wherein step (a) above is performed using a chemical vapor deposition method. 5 The method described by member J, wherein the above chemical vapor deposition method is completed using a Cu (hfac) L chemical compound. 17. A method for forming a copper layer on a material layer on a wafer, the The method includes at least the following steps: (a) placing the wafer in a processing chamber; (b) chemical vapor deposition of copper on the material layer while the wafer is in the processing chamber; and (c) when the wafer is in the processing chamber At the same time, the copper is processed so that the copper adheres to the upper surface of the material layer. The method described in item 17 of the invention, wherein step (c) above includes the steps of: forming a plasma, wherein the plasma contains ions that impact the copper. 1 9. As claimed in item 17 of the scope of patent application The method described above, wherein the material layer mentioned above is a diffusion barrier layer. Page 20 This paper size applies the Chinese National Standard (CNS) A4 specification (UOX297 mm) i- _ 二 I-女. 尺 〆- -II pup —-1-I ^ 1 ^ 11--I-丨 _ (Please read the precautions on the back before filling out this page) 4 'j_4⑽ A8 B8 C8 D8 Printed by ττ and applied by the staff consumer cooperative of the Central Bureau of Standards, Ministry of Economic Affairs Patent scope 20. The method described in claim 17 of the patent scope, wherein the above plasma is formed using a gas mixture containing an inert gas. 2 1. The method described in claim 20 of the patent scope, wherein the above The inert gas has an atomic mass close to the atomic mass of copper. 2 2. The method as described in item 20 of the scope of the patent application, wherein the above inert gas is a gas consisting of argon, krypton, and xenon groups Selected. 23 As described in item 20 of the scope of patent application Method, wherein the above-mentioned gas mixture comprises at least one gas, which is selected from the group consisting of argon, krypton, xenon and hydrogen. 24. The method as described in item 17 of the scope of the patent application, further comprising steps: (d) While the crystals are in the processing chamber, copper is deposited on the copper deposited in step (b). 25. The method as described in item 24 of the patent application scope, wherein step (d) above uses a chemical vapor deposition method Do it. 26. The method described in claim 25, wherein the chemical vapor deposition described above is performed using a Cu (hfac) L chemical compound. 27. — A computer-readable medium containing a program for use on a semiconductor wafer. Page 21 This paper applies the Chinese National Standard (CNS) Λ4 specification (210X2M mm). (Read the precautions on the back first.) 'Re " Write this page-Printed by the Consumers' Cooperative of the China Standards Bureau of the Ministry of Online Economics and Printing 414813 g C8 D8 VI. Patent Application Circular Processing System This system includes a chamber for performing chemical vapor deposition and a A computer controlled by chemical vapor deposition in the room, when the program is executed by the computer, causes the semiconductor wafer processing system to perform the following steps: deposit a copper seed layer on a substrate; supply processing gas to the room ; The processing gas is stimulated to become a plasma, and the copper seed layer is bombarded with ions. 28. The computer-readable medium described in item 27 of the patent application scope further includes a program, which is executed by a computer In order to make the semiconductor wafer processing system, perform the following steps: deposit a copper layer on the copper seed layer. 2 9. The method according to item 2 of the patent application scope, wherein the plasma is formed using hydrogen. 3 0. The method as described in item 18 of the scope of patent application, in which the plasma is formed using hydrogen. (Please read the note on the back before filling in the dome page * " line page 22 This paper size applies to China Kneading standard (CNS) Α · 4 size (210X29? Mm)
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